Flame resistant and mildew resistant composition for cellulose fibers and fabrics



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FLAM]; RESISTANT ANp' MrLpEW RESIST- aNr COMPOSITION roa cELLuLosE means AND FABRICS ,rti'iliit hit" LitLiiCE oFncE Richard .D. Vartanian, Bound Brook, N. ..I., as-

signor to American Cyanamid Company, New York, N. Y a corporation of Maine NoDrawing, ApplicationDecember 7,1949,

Claims.

This invention relates to the treatment of fabrics to produce .a high degree of mildew and flame-resistance, prevent after glow and impart the desired color. In particular, the invention relates to a new group of .novel oil-jin-water type emulsions, and to their preparation and use, whereby coloring, mildew-proofing and flameresisting materials together with after-glow preventatives can be deposited on .a fabric from an aqueous medium in .a single treatment. The instant application constitutes a continuation-inpart of my copending application Serial No. 633,853, .filed December 8, 19.45,, now abandoned.

Coloring of fabrics by padding and printing is one of the oldest :arts. Mildew and/or flameproofing of fabrics to be used for purposes of decoration and/or concealment, though .a newer art, has come .to .be widely demanded. Where not only color but mildew, flame and afterglow resistance are required .in .the same fabric the processing steps required have in many cases been complicated expensive and often unsatisfactory. This has been due to the necessity for separate and successive operations, which in turn were required because the practice of imparting these properties often involved the use of incompatible materials. Even successive treatments were not wholly successful because of the adverse effect of the subsequent treatments on the coloration, and vice versa.

Because of this situation, much work has been done in attempts to combine these operations into fewer processing steps. Here again, incompatability of the materials introduced man difficulties. On the whole, such procedures, like the earlier successive treatments, were either unsuccessful or unsatisfactory for one or more reasons such as: expense; alteration of the hand; limited color range; requirement of excessive amounts of volatile organic solvents .or a substantially all solvent system; physical difficulty or fire hazard Serial No. 131,690

in application; requirement of special drying techniques; lack of light fastness; lack of crockresistance; lack of permanence of flame-resistance; inability to stand weathering; wastefulness in use or application; and difficulty in changing the color to be applied or in cleaning the apparatus used.

There remains then, a demand for a procedure whereby color, mildew, flame and afterglow resistance can be imparted in a, simple, eiiective, and relativell inexpensive treatment. Such a process and material for use therein should be free from the objectionable difilculties noted above and should not result in the production of articles which are subject to such objections.

It is, therefore, the principal object of the present invention to produce a novel composition adapted to deposit the desired coloring, mildew-proofing, flame-proofing and afterglowpreventing materials on the fabric in a single treatment and from an aqueous medium. It is also an object of the invention to devise a treating process which is adapted to handle a wide range of colors without being subject to color distortion by the flame proofing. It is a still further objectto produce articles which have a soft flexible hand and are capable of withstanding extended weathering without excessive loss of either color, flame or mildew resistance.

In accordance with the present invention these and other objects are accomplished by the manufacture and use of novel oil-in-water emulsions. Successful use of such materials to solve the problem completely is quite remarkable in view of the diversity of materials used, the lack of water-solubility of the majority of them and the fact that similar attempts using common solvents lead to many complications.

While the present invention is not primarily intended to be limited to particular materials, certain basic ingredients are commonly found therein. These ingredients may be roughly grouped into types. First, there is the question of the external medium, which in the present invention is aqueous and preferably thickened. Second, is a group of flame-proofing ingredients which include suitably proportioned quantities of a properly halogenated organic material and a fire-resistant, uncolored pigment potentially reactive therewith. Third, is the coloring material which in the present invention is .a pigment or a group of pigments. Fourth, is the group of mildew-proofing agents. Fifth, is the materials which impart afterglow resistance. Finally, because colored pigments have no affinity for the fabric, a binder must be provided therefor. These are basic constituents which are present whether or not additional components are used.

As has been noted, for the continuous phase an aqueous medium is used, and preferably one which is suitably thickened. For this thickening a water-soluble material should be used which itself is colorless but which may be deposited on the fabric to be treated. In accordance with the present invention, the use of a lower alkyl cellulose derivative such as methyl cellulose or Methocel has proved wholly satisfactory. In using methyl cellulose it has been found, for example, that about a 0.5% solution of a 3000-4000 centipoise grade is very effective for most purposes. However, if so desired, other commercially SEAREH ROQM sarily added at one time.

available hydrophilic colloids such as. for example, sodium alginate, water-soluble salts of polyacrylic acid, ammonium caseinate, carboxymethylcellulose and the like or various gums such as tragacanth, karaya, locust bean and the like may be used. When other thickeners are used the amount should be such as to produce an approximately similar viscosity. Because of the difference in weights of these materials as well as their diifering effect on the viscosity when in solution, the amount of such hydrophilic col loid used will vary, usually between about 0.1 and by weight, based on water.

Because the principal composition is an oilin-water type of emulsion it is often desirable, although not always necessary, that the continuous phase contain dispersing and/or emulsifying agents to maintain the necessary interfaces between the phases. Preferably these take the form of water-soluble soaps, for example, ammonium oleate, ammonium stearate and the like. For most purposes the ammonium soaps are preferable to those of sodium or potassium. Not all the soap or soap-forming ingredients are neces- As shown in the exam les, the amount of fatty acid used will be 0.75-0.9% oleic acid or its equivalent. Since the saponifying NH: is present, multiplying these values by the ratio of their molecular weights it will be seen that this will provide about 0.8-l.l% by weight of the pad bath emulsion as ammonium oleate or a proportionate weight of its equivalent. This constitutes a good average practice although as little as 0.25% or as much as 4.0% may be used. Instead of fatty-acid soaps. other materials such for example as ammonium caseinate; sulfonated oils such as sulfonated castor oil, mahogany soap and the like; and

sulfated materials such as the sodium salt of the sulfated higher aliphatic alcohols may be used. When such emulsifying agents are present, it is desirable that the external medium be alkaline. This is readily accomplished by adding aqueous ammonia or an organic base such as morpholine or the like. For this reason, as shown in the examplea more ammonia, or its equivalent, is added than is required to saponify the fatty acid used. Usually enough is added to provide about 1.0-1.7% by weight of the pad bath emulsion as 28% NH4OH.

These dispersing and/or emulsifying agents may be added per se to the continuous phase. If so, they may be conveniently added along with the hydrophilic colloid. 0n the other hand, it may be desirable to form these constituents in situ. In the latter case it is usually desirable to add only the alkaline component to the water phase and to add the fatty acid component with the dispersed phase. In this Way the two components can react and form the desired agent at the interface between the continuous and dispersed phases during the incorporation of the latter.

Having prepared the thickened aqueous material for the continuous phase, the dispersed phases containing the halogenated organic material, the flame-resistant pigment, the resin binder, the coloring pigments and in some cases the afterglow preventative are prepared. These are then added usually stepwise, to the aqueous material and the whole blended into a smooth, stable heterogeneous emulsion. For the best results, so far as practical application is concerned. blending should be continued until the bulk of lent.

4 the dispersed material is reduced to a size of approximately 30 microns or less.

With regard to the flame-proofing ingredients, the nature of the chlorinated organic hydrocarbon used may be quite widely varied. It should, however. possess certain properties. In particular, it should be substantially colorless, fire-resistant, water-insoluble, readil available or easily prepared. Preferably it should be a fluid. However, materials which are semi-fluid, that is, of waxy consistency may be used by adding thereto a sufficient amount of a suitable solvent thinner to impart the requisite fluidity. Several materials are well suited for use as flame-proofing ingredients.

partially polymerized chlorobutadiene (neoprene), for example, have proved to be particularly well suited for the purpose. Other useful materials include for example, polyvinyl chloride, chlorinated naphthalene, chlorinated tricresyl phosphate and the like. Iii''amount, it will coHsti'tutefibout 530% of the pad bath, depending on the halogen content. Enough to provide about 242% available halogen should be used. Chlorinated products are those most generally employed because of their availability but use of the other halogens is perfectly feasible. As shown in the examples from about 5.41 parts of 80% solution of a 60% chlorinated product .3% by weight of pad bath) to about 15% of a 40% chlorinated product may be used. These are commercial products and vary plus or minus a few per cent in chlorine content. Based on 42%:1% and 60%:1% content, enough materials are there used to provide 2.56-6.4% or about 2.6-6.4% of the pad bath emulsion of combined chlorine available to liberate I-ICl when heated to combustion temperatures.

Similarly, the flame-resistant pigment may be varied if so desired. It should, however. be one which not only is compatible with the emulsion but also is colorless or white or only lightly colored so as not to affect adversely the coloration obtained from the color-producing materials. Finally, it must be one which when used with the halogenated material is effective to impart flameresistance. Such pigments as calcium or magnesium carbonate or the like have been used. Other suggestions include zinc borate, magnesium ammonium phosphate, melamine pyrophosphates and the like. However, finely-powdered antimony oxide has proved generally superior in use and is therefore preferred. As shown below, about 63-15% by weight of the padding emulsion should comprise antimony oxide. will vary somewhat depending on the molecular weight of the specific pigment chosen where some equivalent is substituted.

These flame-proofing materials are usually compounded into the final emulsion as a unit by first blending together the chlorinated material and the pigment. In so doing, a small amount of a volatile solvent, usually a hydrocarbon solvent, is used to thin the chlorinated material slightly. Where the emulsifying agent-is formed in situ it is well to add at least part of the acidic constituent therefor with the flame-proofing material. In such cases, a small amount of some soap-forming acidic material such as linseed-oil fatty acids, oleic acid or the like, therefore also is conjointly added. Only a sufficient amount of solvent should be used to impart the requisite fluidity since the principal purpose of this operation is to assist in the eventual compounding of Chlorinated paraffin is excel- Certain chlorinated elastomers, such as ial'iljdfi ii; iii illiliZFi-lzii the final emulsion and excessive amounts of volatile solvents a e neither necess ry nor desira le.

Since pigments have no afiinity for the fabrics it is necessary to provide some binder to effect a pigment-fibre attachment bond. Again the invention has the advantage of not being limited to specific materials. In the case of the: fireresisting pigments at least part of this bonding action may be provided by the chlorinated material. Particularly is this true when using polymerized chlorinated b-utadienes. However, added bonding action may be and usually is required. Further, the coloring pigments, which are added apart from the flame-proofing ingredients must be also made to adhere to the fabric. As a consequence, some added binders must be used to attach the coloring pigments and aid in holding the flame-resisting pigments.

Since flame-proofing is not the sole object but rather one of the principal objects, imparting color to the emulsion, and to the products treated therewith, is an important feature. In accordance with the present invention, color is added to the emulsion and eventually applied to the fabric as a finely-divided pigment. Not only does this have the advantage of providing light fastness in a wide range of colors but it obtains this advantage without the necessity for the various processing treatments required when coloring is done by a dyeing. Substantially any solid, finely-divided, colored, light-fast pigment may be used if so desired. In the exemplary mater al given below TB-8.1% by weight of chrome oxide green is used. This amount will vary somewhat, according to the nature and size of the pig ment molecule. y

In addition to the problem of making the material resistant to active combustion from an open flame, it is desirab e to prevent afterglow, i. e., the tendency of the fibre ends to smolder even when open flame no longer is present. Particularly is this desirable in fabrics or net materials to be used in warfare. The more effective types of agent for this purpose include both inorganic phosphates such as ammonium phosphate, dihydrogen ammonium phosphate, sodium ammonium phosphates, and phosphates of such compounds as guanidine, dicyandiamide, melamine and the like. As shown below, about 1.0-1.'75% by weight of the padding emulsion should comprise diammonium hydrogen phosphate or an equivalent weight of one of the equivalent materials. 15% should be used.

These materials usually are soluble in water and are added to the final emulsions as part of the continuous or water phase in which they are dissolved. Fabrics impregnated therewith ordinarily would not be expected to be resistant to weather. The degree to which the treatment with these materials is retained when they are applied as constituents of the novel emulsions of this invention, in which they are quite compatible, is therefore wholly surprising. While these materials are preferred, other materials, particularly those liberating nitrogen at flame temperatures or lower, such asthe water-soluble resins derived from urea or melamine and the like, may also be effectively used. While the added binders may bevaried, they are subject to certain limitations. Heat-convertible resins are preferred. Because color is important, the

" binder should be substantially colorless or of a light shade. It should be unconverted, stable against conversion in the emulsion at normal temperatures and capable of deposition with the not exceed the values given above.

coloring pigment from the emulsion. If the fabric has had some pretreatment the binder must be one compatible with any residual material therefrom. Preferably, too, it should be easily converted to a water-insoluble form without any appreciable heating beyond that required in drying the fabric to which the emulsion has been applied.

In accordance with the present invention, it has been found that many heat-convertible alkyd resins, particularly drying-oil-modified alkyds are well suited for this purpose as are many organic solvent soluble amide-aldehyde resins, particularly the alkylated resins such as butylated ureaformaldehyde resin or butylated melamine-formaldehyde resin. Preferably, in order to insure binding while maintaining the optimum flexibility in the finished product, a mixture as of oil-modified alkyd and amide-aldehyde resins is used. As is brought out in the examples, a good average practice is to use 0.9-'1.0% by weight of the amide-aldehyde resin and about 2.65-2.95% or about 2.6-3.0% by weight of the alkyd resin. These are eouivalent to' a total resin content of about 3.540% and averaging about 3.75%.

Usually about 05-10% is used.

in blending the flame-resisting materials, to assist in forming the emulsifying agent, a small quantity of an acidic soap-forming material such as a fattv acid is added. A basic soap-forming constituent such as a small amount of aqueous ammonia is also added to su lement t at in the external phase. Again the total amounts should Further, this may be supplemented as desired by additional emulsifying and/or dispersing agents such as pine oil, terpineol, terpenes and the like, if so desired. As shown below, from about 0.23-0.5% by weight of pine oil or the corresponding amount of its equivalent constitutes a good average practice.

As noted above, mildew-proofing is an essential feature of the present invention. It is an advantage of the invention that it is flexible in that the incorporation of the mildew-proofing agents may take any one of several different forms. The preferred mildew-proofing agents may be of the oilor solvent-soluble type or a water-soluble type. The nature of the final emulsion as well as the method of incorporating these agents will depend on which type is chosen.

Use of the water-soluble type of mildew-proofing agent is the simplest, so far as the actual incorporation is concerned and will be considered first. Typical agents of this type include the alkali metal salts of halogenated phenols and cresols, such, for example, as sodium chloro-ophenyl phenate, sodium pentachlorophenate and the like. Being water-soluble these compounds are readily incorporated into the continuous phase during the preparation of the dispersing medium therefor. For comparison, since they are added to the water along with the thickening agent, the amounts required will range from about 2-4 times the latter or about 6.3-2.0% of the pad bath. While these materials are watersoluble, their deposition on the fabric in accordance with the present invention produces asurprisingly stable permanent treatment.

The oil or solvent-soluble types of mildewproofing agent in general constitute those phenols, the alkali metal salts of which were noted above as water-soluble types. They may be incorporated into the final emulsion in either of two.

ways. First, the mildew-proofing agent may be dissolved in the fiame-proofing-solvent mixture. When the latter is blended in the final emulsion, the mildew-proofing agent remains therein and constitutes one component of the dispersed phase which also contains the chlorinated organic material, the flame-resistant pigment, the solvent thinner, and the emulsifying material. Second, the mildew-proofing agent may be dissolved in a soluble oil such as sulfonated castor-oiland the like. Usually a small amount of ammonium hydroxide is added, particularly in those cases in which the emulsifying and/or dispersingagents are formed in situ. This mixture, or rather solution, is added to the water at the time the dispersing medium is being prepared. It is generally assumed to become a part of the continuous phase. There is a possibility, however, that a part of the mildew-proofing agent does separate out and becomes a separate dispersed phase.

It will be seen, therefore, that the principal feature of the present invention is an oil-in-water type emulsion in which the external aqueous medium is usually thickened somewhat to increase its viscosity and assist in maintaining permanent dispersion. In addition, this dispersing medium also contains the afterglow preventative, and in some cases the mildew-proofing material. Emulsified in the aqueous medium are a suitably chlorinated organic hydrocarbon, a flame-resistant pigment, a resin binder, a coloring pigment or pigments, and in some cases also the mildewproofing agents. In addition thereto, there may be added various supplementary ingredients such as dispersing or emulsifying constituents, additional fire-proofing agents and the like.

While the emulsion as a whole is substantially a stable heterogeneous composition, it does not consist solely of water as the single dispersion medium with a number of individual ingredients separately suspended therein. Rather, there are present one or more dissolved or colloidally suspended ingredients in the water, which solu- Example 1 A colloidal solution consisting of 2 parts of methyl cellulose (4,000 centipoises), parts of aqueous ammonia (28%) and 215 parts of water was prepared. To this was added a solution consisting of 300 parts of chlorinated paraffin (40% Cl), 15 parts of oleic acid and 10 parts of pine oil in 50 parts of a petroleum hydrocarbon solvent (B. P. 135-187 0., containing 90% aromatics) to which solution 300 parts of antimony oxide (325 mesh) had been added. The mixture was emulsified by high speed stirring and to the resultant oil-in-water emulsion, under continued stirring, was added 8 parts of sulfonated castor oil and 20 parts of diammonium hydrogen phosphate in parts of water, to which 5 parts of aqueous ammonia (28% NH3) have been added.-

The resultant emulsion was diluted with water under' stirring to a solids content of about 32.2% which gave a suitable viscosity for padding. The fabric was dipped in this emulsion, passed through rubber squeezed rolls and dried at 90 C. for about 1 hour. The fabric weight increase amounted to about 40% (dry basis) and the treated fabric was flame-resistant to a marked degree both before and after accelerated weathering.

Example 2 To a solution consisting of 14 parts of a chlorinated paraffin (40% Cl), 0.4 part by weight of oleic acid, 0.5 part by weight of steam distilled pine oil, and 3 parts by weight of a petroleum hydrocarbon (B. P. 135-177 C., containing 90% aromatics), was added by high speed stirring, 14 parts of antimony oxide. This mixture was emulsified by means of high speed stirrin in a solution consisting of 0.2 part of methyl cellulose (4,000 cps. grade), 0.5 part of ammonium hydroxide (28% N163) and 23.7 parts of water. To the resulting oil-in-water emulsion was added 27 parts of a milled color base consisting of 1.4 parts of ammonium hydroxide (28%), 1.4 parts of oleic acid, 16.2 parts of chrome oxide green, 2.1 parts of a 50% solution of butylated dimethylol urea in a mixture of xylene and butanol, and 5.9 parts of a solution of a drying-oil modified alkyd resin in pine oil. To this was stirred in a solution containin 1.2 parts of chloro-ortho-phenyl phenol, 1.5 parts of sulfonated castor oil and 0.6 part of ammonium hydroxide (28%) Finally, a solution containing 3.5 parts of diammonium hydrogen phosphate, 0.9 part of ammonium hydroxide (28%), and 9 parts of water at 40 C. wa added slowly with high speed stirring. The resulting oil-in-water emulsion was diluted with an equivalent weight of water giving a padding emulsion with a solids content of 28.7%. The viscosity of this diluted colored emulsion was suitable for padding. A sample of shrimp netting was dipped in this emulsion, squeezed between rubber rolls to remove the excess of pad liquor, and finally dried at C. for 60 minutes. The dry pick up on the netting was 53% solids and the netting was flame-resistant and showed no afterglow both before and after accelerated weathering. The netting was also resistant to mildew growth.

Example 3 To a solution consisting of 12 parts of an 80% solution of chlorinated parafiin (60% C1) in a petroleum hydrocarbon (B. P. -177 C. and 92% aromatics), 0.4 part of oleic acid, 0.5 part of steam distilled pine oil and 3 parts of the petroleum hydrocarbon, was added with high speedstirring 14 parts of antimony oxide. This mixture was emulsified by high speed stirring in a solution consisting of 0.2 part of methyl cellulose (4,000 cps), 0.5 part of ammonium hydroxide (28%) and. 25.7 parts of water. To the resulting oil-in-water emulsion was stirred in 27 parts of a milled color base consisting of 1.4 parts of ammonium hydroxide (28%), 1.4 parts of oleic acid, 16.2 parts of chrome ox- SEARCH UUEV! V ide green, 2.1 parts of a 50% solution of hutylated dimethylol urea in a mixture of xylene and butanol, and 59 parts of a 70% solution .of a drying-oil modified alkyd resin in pine oil. To this was stirred in a solution containing 1.2 parts of chloro-ortho-phcnylphenol, 2.0 parts of sulfonated castor oil and 0.6 part by weight of ammonium hydroxide (28%). Finally, a solution containing 3 parts of diammonium hydrogen phosphate, 0.9 part of ammonium hydroxide (28% NH3) and 9 parts of water at 40 C. was added slowly with high speed stirring. The resulting oil-in-water emulsion was diluted by stirring in 122 parts of water leaving a solids content of 24%. A pad dyeing was made on shrimp netting with this emulsion as described in Example 2. The dry pick up was 49.2% solids and the netting showed similar properties to that padded for Example 2.

The above examples correspond to the following formulation:

Per Cent Weight in Pad Bath Ingredients Ex. 1 Ex. 2 Ex. 3 Min. Max.

Chlorinated Paraflin:

40% (42%:l:1%).- l5 (chlorine content) (6.1 6. 4) 40% 7.0 (2187 3.18) 60% (60%=|=1%) 4. 33 (2. 56 2. 64)

Methyl Cellulose 0.1 0.1 0.09 .09 0.1 Oleic Acid 0. 75 0.2 0. 18 O, 2 O. 75 28% NHAO 1.0 1.0 0.90 .09 0.1 Pine Oil 0.5 0.25 0.23 0. 23 O. 5 Solvent 2.5 1.5 1.35 1.35 2.5 Antimony xide l 7 6. 32 6. 3 Water 63. 75 66. 35 70. 58 63. 8 70. 6 Sulfonated Castor Oil 0. 4 0. 75 0.9 0. 4 0.9 Soluble Phosphatd 1. O 1. 75 1. 35 1. 0 1. 75 Mildew-proofing 0. 6 0. 54 0. 5 0. 4 Color Base 13. 12.15

Color Base Composition: 28% NH4OH 0.7 0. 63 0. 63 0. 7 Oleic Acid 0. 7 0. 63 0. 63 0. 7 Chrome Green Oxide 8.1 74 3 7. 3 8. 1 Urea-formaldeh y d e r e s i n (Beetle 219-8) 1.05 0. 94 0. 9 1. 05 Alkyd resin Rezyl 419-9) 2. 95 2. 2. 65 2. 95

Total Oleic Acid 0. 0. 9 0.81 0. 75 0. 9 (As A m s l (0 8) (1 1) oap Total 28% NH4OH 1.0 1.7 1.53 1.0 1.7

I claim:

1. A stable heterogeneous oil-in-water type emulsion, adapted for the simultaneous deposition on fabrics of mildew-proofing, fire-resisting, afterglow-preventing, coloring and binding materials from an aqueous medium, which emulsion is comprised of a continuous dispersion 'medium comprising water containing 0.1-10% by l0 vertible'resin binder selected from the group consisting of (a) the drying-oil-modified alkyd resins, (b) organic-solvent-soluble amide-aldehyde resins, and (0) mixtures thereof, and at least one coloring pigment; 0.25-4.0% of a water-soluble soap of a fatty acid and 0.32% of "g, haloge i ated p engLmildew-proofig agent disnhzed fii a watef soluble sulfonated oil, the percentages given being percent by weight of the total emulsion.

2. A composition according to claim 1 in which the hydrophilic colloid is a. water-soluble alkyl cellulose and the mildew-proofing agent is a wator-soluble alkali metal salt of a halogenated phenol dissolved in the continuous phase.

3. A composition according to claim 1 in which the hydrophilic colloid is a water-soluble alkyl cellulose and the mildew-proofing agent is principally present in the water phase as a halogenated phenol dissolved in a Water-soluble sulfonated oil.

4. A composition according to claim 1 in which the hydrophilic colloid is a water-soluble alkyl cellulose and the mildew-proofing agent is a halogenated phenol present as a component of the dispersed phase containing the fire-resisting materials.

5. A stable heterogenous oil-in-water type emulsion, adapted for the simultaneous deposition on fabrics of mildew-proofing, fire-resisting, afterglow-preventing, coloring and binding materials from an aqueous medium, which emulsion is comprised of a continuous dispersion medium comprising water containing 0.1-10% of a hydrophilic colloid and 1-5% of a Water-soluble phosphate afterglow preventative; a dispersed phase comprising 5-30% of a film-forming, non-volatile chlorinated paraflin containing 2-12% of combined chlorine and capable of liberating HCl at elevated temperatures 6-15% of finely-divided antimony oxide and an organic solvent; a separately dispersed phase comprising an organic solvent 0.5-10% of an uncured, heatconvertible, resin binder selected from the group consisting of (a) the drying-oil-modified alkyd resins, (b) organic-solvent-soluble amide-aldehyde resins, and (0) mixtures thereof and at least one coloring pigment; 0.25-4.0% of a watersoluble soap of a fatty acid; and 03-20% of a halogenated phenol mildew-proofing agent dissolved in a water-soluble sulfonated oil, the percentages given being percent by weight of the total emulsion.

6. A method of producing a stable heterogeneous oil-in-water type emulsion, adapted for the simultaneous deposition on fabrics of mildewp-roofing, fire-resisting, afterglow-preventing, coloring and binding materials from an aqueous medium which comprises the steps of preparing an aqueous medium by dissolving therein about 0.1-10% of a hydrophilic colloid, 0.25-4.0% of a water-soluble soap of a fatty acid, 1-5% of a water-soluble phosphate afterglow preventative and suiiicient alkaline material to maintain an alkaline pH; blending into a smooth paste a mixture comprising 5-30% of a film-forming, substantially colorless, water-insoluble, non-volatile chlorinated organic material containing 2-12% of combined chlorine and capable of liberating HCl at elevated temperatures; 6-15% of a colorless fire-retarding pigment and only a sufilcient amount of an organic solvent to impart fluidity; blending into a smooth paste a mixture of a solution of 05-10% of an uncured, heat-convertible resin binder selected from the group conll sisting of (a) the drying-oil-modified alkyd resins, (b) organic-solvent-soluble amide-aldehyde resins, and (0) mixtures thereof in approximately the minimum amount of a solvent therefor and at least one coloring pigment; separately stirring the pasted materials and 03-20% of a halogenated phenol mildew-proofing agent dissolved in a water-soluble sulfonated oil into the aqueous medium, and continuing the stirring action for a sulficient time to blend the whole into a smooth, heterogeneous emulsion in which the dispersed material is substantially all reduced Y to a size not greater than 30 microns, the perw we 12 alkali salt of a halogenated mononuclear aryl alcohol.

10. A process according to claim 6 in which the emulsifying agent is an ammonium soap of a higher fatty acid formed in situ by adding the acidic component to the aqueous medium and adding the basic constituent with the dispersed phase.

RICHARD D. VARTANIAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 7 2,089,697 Groebe Aug. 10, 1937 2,178,625 Clayton Nov. 7, 1939 2,292,423 Yohe Aug. 11, 1942 2,316,496 White Apr. 13, 1943 2,326,233 Leatherman 'Aug. 10, 1943 OTHER REFERENCES Chemical Industries article by Scheer, vol. 54, No. 2, February 1944, pp. 203-205. 

1. A STABLE HETEROGENEOUS OIL-IN-WATER TYPE EMULSION, ADAPTED FOR THE SIMUTANEOUS DEPOSITION ON FABRICS OF MILDEW-PROOFING, FIRE-RESISTING, AFTERGLOW-PREVENTING, COLORING AND BINDING MATERIALS FROM AN AQUEOUS MEDIUM, WHICH EMULSION IS COMPRISED OF A CONTINUOUS DISPERSION MEDIUM COMPRISING WATER CONTAINING 0.1-10% BY WEIGHT OF A HYDROPHILLIC COLLOID AND 1-5% OF A WATER-SOLUBLE PHOSPHATE AFTERGLOW PREVENTATIVE; A DISPERSED PHASE COMPRISING 5-30% OF FILMFORMING SUBSTANTIALLY COLORLESS WATER-INSOLUBLE NON-VOLATILE CHLORINATED ORGANIC COMPOUND CONTAINING 2-12% BY WEIGHT OF THE EMULSION OF COMBINED CHLORINE AND CAPABLE OF LIBERATING HCL AT ELEVATED TEMPERATURES, 6-15% OF A COLORLESS, FIRERETARDING PIGMENT, AND AN ORGANIC SOLVENT; A SEPARATELY DISPERSED PHASE COMPRISING AN ORGANIC SOLVENT, 0.5-10% OF AN UNCURED, HEAT-CONVERTIBLE, RESIN BINDER SELECTED FROM THE GROUP CONSISTING OF (A) THE DRYING-OIL-MODIFIED ALKYD RESINS, (B) ORGANIC-SOLVENT-SOLUBLE AMIDE-ALDEHYDE RESINS, AND (C) MIXTURES THEREOF, AND AT LEAST ONE COLORING PIGMENT; 0.25-4.0% OF A WATER-SOLUBLE SOAP OF A FATTY ACID; AND 0.3-2% OF A HALOGENATED PHENOL MILDEW-PROOFING AGENT DISSOLVED IN WATER-SOLUBLE SULFONATED OIL, THE PERCENTAGES GIVEN BEING PERCENT BY WEIGHT OF THE TOTAL EMULSION. 